CN108822159B - Asymmetrical substitute iron iron hydrogenates enzyme mimics and its photochemical syntheses method and application - Google Patents
Asymmetrical substitute iron iron hydrogenates enzyme mimics and its photochemical syntheses method and application Download PDFInfo
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- CN108822159B CN108822159B CN201810882497.2A CN201810882497A CN108822159B CN 108822159 B CN108822159 B CN 108822159B CN 201810882497 A CN201810882497 A CN 201810882497A CN 108822159 B CN108822159 B CN 108822159B
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- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 37
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 61
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000004088 simulation Methods 0.000 claims abstract description 44
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 30
- 125000003368 amide group Chemical group 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000005864 Sulphur Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- -1 amido Phosphine Chemical compound 0.000 claims description 14
- 238000004809 thin layer chromatography Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 8
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 238000012544 monitoring process Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000012746 preparative thin layer chromatography Methods 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000003003 phosphines Chemical class 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000000039 preparative column chromatography Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000003446 ligand Substances 0.000 abstract description 33
- 230000003197 catalytic effect Effects 0.000 abstract description 30
- 238000002360 preparation method Methods 0.000 abstract description 16
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 abstract description 9
- 108010072136 iron hydrogenase Proteins 0.000 abstract description 7
- 229910001139 Telluric iron Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000006606 decarbonylation reaction Methods 0.000 abstract description 4
- 230000003592 biomimetic effect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000010992 reflux Methods 0.000 abstract description 3
- 230000006324 decarbonylation Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 25
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 13
- 229910052698 phosphorus Inorganic materials 0.000 description 13
- 239000011574 phosphorus Substances 0.000 description 13
- 230000009467 reduction Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000007848 Bronsted acid Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000013522 chelant Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 229940087654 iron carbonyl Drugs 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000004437 phosphorous atom Chemical group 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- 238000007172 homogeneous catalysis Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910004373 HOAc Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000005588 protonation Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000007445 Chromatographic isolation Methods 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 241000736199 Paeonia Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0208—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to biological enzyme biomimetic chemistry and new energy materials fields, and the double phosphine chelatings of the amido specifically containing different disulphide bridges bases replace iron iron hydrogenation enzyme mimics and photochemical syntheses method and application.The three classes of the analogies more fully chemical simulation native iron iron hydrogenase catalytic active center are containing the basic structure and catalysis of different two iron of trimethylene base, the two butterfly-shaped skeletons of sulphur.Photochemical syntheses method of the invention aoxidizes for decarbonylation method and heating reflux method compared to common, its preparation manipulation is easy, reaction condition is mild, reaction rate is efficient, product is single and yield is moderate, is suitably adapted for preparing a variety of bidentate ligand Asymmetrical substitute iron iron hydrogenation enzyme mimics.
Description
Technical field
The present invention relates to biological enzyme biomimetic chemistry and new energy materials fields, and the amido specifically containing different disulphide bridges bases is double
Phosphine chelating replaces iron iron hydrogenation enzyme mimics and its photochemical syntheses method and catalytic applications.
Background technique
Hydrogen is the optimum fuel of next-generation cleaning and renewable energy.Existing hydrogen producing technology have chemical catalysis cracking,
Optical electrical chemical catalysis decomposes water etc., and wherein electrochemical techniques have many advantages, such as high conversion efficiency, environmentally protective, thus obtain extensively
General use.Currently, noble metal platinum is the optimum catalyst for industrializing water electrolysis hydrogen production, however it is expensive and resource is dilute
It is few, so finding the non-precious metal catalyst of high catalytic activity and being applied to the hydrogen manufacturing of optical electrical chemical catalysis is current new energy material
The research hotspot in material field.In nature, native iron iron hydrogenase is because there are unique catalytic active center [Fe for it2(μ-
SXS-μ)(CO)3(CN)2] (disulphide bridges base X=CH2N(H)CH2, azepine trimethylene base；CH2CH2CH2, trimethylene base；CH2OCH2, oxa-
Trimethylene base) this basic structure is that proton catalysis is reduced into hydrogen and the highest biological enzyme of catalytic efficiency so far.It is based on
This, researcher has carried out extensive biology to the basic structure and catalysis of native iron iron hydrogenase catalytic active center
Enzyme biomimetic chemistry research, and design and be prepared for a series of iron iron hydrogenation enzyme mimics containing different disulphide bridges bases.In these simulations
In object, the Asymmetrical substitute iron iron hydrogenation enzyme mimics that bidentate ligand is coordinated in the same iron atom in a manner of chelating have been recognized
Realize efficient catalytic proton reduction at the ideal non-precious metal catalyst of hydrogen to be that one kind is most potential.Currently, asymmetry takes
The synthetic method that Dai Tietie hydrogenates enzyme mimics is mainly two kinds: one is aoxidized using trimethylamine oxide/acetonitrile system
Decarbonylation reaction, another kind are to carry out being heated to reflux decarbonylation reaction using benzene kind solvent system.However, being utilized in document report at present
Above two method only prepares the Asymmetrical substitute iron iron hydrogenation enzyme mimics of base containing trimethylene or ethylene group, not yet reports so far
The Asymmetrical substitute iron iron hydrogenation enzyme mimics of nitrogen-containing hetero trimethylene base or oxa- trimethylene base are crossed in road.For above two synthetic method
For, the first due to raw material substrate structure and ingredient proportion difference, will cause different degrees of by-product in use
Generate and increase the complexity of separation principal product；Second in use since raw material substrate and products therefrom are for adding
The stabilization gender gap of hot temperature will cause raw material and the different degrees of decomposition of product and cause product yield lowly even zero,
Such as the raw material substrate of nitrogen-containing hetero trimethylene base just easily decomposes very much in heating benzene kind solvent.In addition, amido is double in bidentate ligand
Phosphine is a kind of cheap and easy to get, adjustable organophosphor ligand of property, contained by nitrogen-atoms and its connected substituent group type adjust
The self property of such ligand, therefore it is a kind of very widely used bidentate ligand in Organometallic Chemistry reaction.
Summary of the invention
The present invention be directed to the analyses of above technology, and solve the defect and more of above two synthetic method use process
For comprehensively two iron two sulfur catalysis of the three classes containing different trimethylene bases from structurally and functionally chemical simulation native iron iron hydrogenase
Activated centre, therefore the application provides three classes containing different disulphide bridges using easy, mild, efficient general " photochemical syntheses method "
The double phosphine chelatings of the amido of base replace iron iron to hydrogenate enzyme mimics, have studied their electro-catalysis using electrochemical cyclic voltammetry and restore
The application of acetic acid proton generation hydrogen.
The present invention is achieved by the following technical solutions: the double phosphine chelatings of the amido of the base containing disulphide bridges replace iron iron hydrogenase
Analogies, the double phosphines of amido in the analogies are coordinated in same iron atom in a manner of chelating, and the analogies chemical formula is Fe2
(μ-SXS-μ)(CO)4{κ2-(Ph2P)2N (R) }, molecular structural formula is as follows:
Wherein X is azepine trimethylene base CH2N(Ph)CH2, ethylene group CH2CH2Or oxa- trimethylene base CH2OCH2；R is N, N- bis-
Methyl-1-propyl CH2)3NMe2Or normal-butyl (CH2)3Me。
Invention further provides the double phosphine chelatings of the amido of above-mentioned three classes base containing disulphide bridges, and iron iron to be replaced to hydrogenate enzyme simulation
The Actinochemical synthesis of object, comprising the following steps:
(1) two iron, two sulphur, six carbonyl-complexes Fe is weighed2(μ-SXS-μ)(CO)6With the double phosphine (Ph of amido2P)2NR is blended in
Together, in a nitrogen atmosphere, toluene solvant is injected, magnetic agitation obtains light red liquid；
(2) under conditions of being protected from light, with the above-mentioned solution of LED light vertical irradiation, 2~3h is reacted at room temperature, TLC monitoring reaction is former
Until material disappears；
(3) vacuum rotary steam remove toluene solvant obtain crude product, with methylene chloride extract residue, use mixed solvent as
Solvent or eluant, eluent carry out preparative thin-layer chromatography or column chromatography chromatogram separation, obtain target simulation object；
Wherein X is azepine trimethylene base CH2N(Ph)CH2, ethylene group CH2CH2Or oxa- trimethylene base CH2OCH2；R is N, N- bis-
Methyl-1-propyl (CH2)3NMe2Or normal-butyl (CH2)3Me。
The double phosphine chelatings of amido invention further provides above-mentioned three classes containing different disulphide bridges bases replace iron iron hydrogenase
The synthetic route of analogies:
In the photochemical syntheses method that the double phosphine chelatings of the amido containing different disulphide bridges bases replace iron iron hydrogenation enzyme mimics, institute
State two iron, two sulphur, six carbonyl-complexes Fe in step (1)2(μ-SXS-μ)(CO)6With the double phosphine (Ph of amido2P)2NR and toluene solvant
Mixing ratio be 0.15~0.25mmol:0.18~0.375mmol:90~100mL.
In the photochemical syntheses method that the double phosphine chelatings of the amido containing different disulphide bridges bases replace iron iron hydrogenation enzyme mimics, institute
The power for stating LED light used in step (2) is 20W and wavelength is 365nm.
When concrete application is implemented, in above-mentioned preparation method, it is 2:3's that the mixed solvent in the step (3), which is volume ratio,
Contain methylene chloride/petroleum ether that the volume ratio of 2~3 drop triethylamines is 2:3 in methylene chloride/petroleum ether mixed liquor or 150mL
The methylene chloride/methanol mixed liquor that mixed liquor or volume ratio are 10:1~20:1.
Preferably, the preparative thin-layer chromatography in the step (3) is silica G thin-layer chromatography, and column chromatography is 200~300
Mesh silica gel column chromatography.
Invention further provides the double phosphine chelatings of the amido of the base containing disulphide bridges, and iron iron to be replaced to hydrogenate enzyme mimics
Or the double phosphine chelatings of amido of the base containing disulphide bridges replace the Actinochemical synthesis of iron iron hydrogenation enzyme mimics to be prepared
Target simulation object be reduced into the application in hydrogen in electro-catalysis Bronsted acid.
The double phosphine chelatings of the above-mentioned amido containing different disulphide bridges bases replace the catalytic performance test of iron iron hydrogenation enzyme mimics to adopt
With classical electrochemical cyclic voltammetry: the test, which utilizes on CHI 660E electrochemical instrument with the glass-carbon electrode of 3mm diameter, is
Working electrode, with platinum filament be to electrode, with non-aqueous Ag/AgNO3(0.01M AgNO3/0.1M n-Bu4NPF6/CH3It CN) is reference
The classical three-electrode system of electrode measures in cylindrical groove and under nitrogen atmosphere；0.05 μm of three oxygen will be used before each test
Change two aluminium powders polishing glass-carbon electrode, then uses ultrasonic cleaning, last acetone rinsing, cold wind drying in water；Test system
Solvent be the acetonitrile of chromatographically pure, sample concentration 1mmol/L, supporting electrolyte is the n- for being 0.1mol/L with concentration
Bu4NPF6, Bronsted acid 0,2,4,6,8,10mmol/L acetic acid；Test gained current potential is the reduction potential corrected through ferrocene.
The catalytic performance shows themselves in that in the electro-chemical test system containing 1mmol/L target simulation object, with proton
Acid concentration is continuously increased, and has the peak current of a reduction peak persistently to increase, and corresponding peak electricity-position variation is little, this phenomenon
The exactly notable feature of homogeneous catalysis liberation of hydrogen.At the same time, the reason of the target simulation object of the base of trimethylene containing oxa- or azepine trimethylene base
The ethylene group target simulation object without hetero atom end of the bridge is apparently higher than by catalytic efficiency TOF.
The double phosphine chelatings of amido of the present invention containing different disulphide bridges bases replace iron iron hydrogenation enzyme mimics relative to existing
Technology has the following beneficial effects:
(1) photochemical syntheses method of the present invention aoxidizes for decarbonylation method and heating reflux method compared to common,
Preparation manipulation is easy, reaction condition is mild, reaction rate is efficient, product is single and yield is moderate, is suitably adapted for preparing a variety of contain
The Asymmetrical substitute difference disulphide bridges base iron iron of different bidentate ligands hydrogenates enzyme mimics.
(2) the three classes analogies prepared by the present invention are to be coordinated in the asymmetry of the same iron atom in a manner of chelating to take
Dai Tietie hydrogenates enzyme mimics, and it is non-expensive at the ideal of hydrogen that they are acknowledged as most potential realization efficient catalytic proton reduction
Metallic catalyst；At the same time, analogies of the prepared three classes containing different disulphide bridges bases more fully simulation from structure
Two iron two sulfur catalysis activated centre of the three classes containing different trimethylene bases in native iron iron hydrogenase.
(3) for the double phosphines of amido used in the present invention for other bidentate ligands, it is a kind of easily prepared, property
Adjustable biphosphine ligand, contained by nitrogen-atoms and its connected substituent group type it is adjustable the electricity of prepared analogies
Son, three-dimensional effect and capture, transfer protons ability, and then functionally more purposefully adjust urging for prepared analogies
Change hydrogen manufacturing performance.
Detailed description of the invention
Fig. 1 is the Fourier transform infrared spectrogram of analogies 1-6 described in 1-6 of the embodiment of the present invention.
Fig. 2 is the nuclear magnetic resonance phosphorus spectrogram of analogies 1-6 described in 1-6 of the embodiment of the present invention.
Fig. 3 is 1 target simulation object 1 (1mM) of the embodiment of the present invention in 0.1M n-Bu4NPF6HOAc in/MeCN solution (0,2,
4,6,8,10mM) the cyclic voltammetry curve figure after sweeps fast 100mV s-1。
Fig. 4 is 2 target simulation object 2 (1mM) of the embodiment of the present invention in 0.1M n-Bu4NPF6HOAc in/MeCN solution (0,2,
4,6,8,10mM) the cyclic voltammetry curve figure after sweeps fast 100mV s-1。
Fig. 5 is 3 target simulation object 3 (1mM) of the embodiment of the present invention in 0.1M n-Bu4NPF6HOAc in/MeCN solution (0,2,
4,6,8,10mM) the cyclic voltammetry curve figure after sweeps fast 100mV s-1。
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Generally, analogies of the invention described method can be prepared through the invention.Following reaction side
Case and embodiment are for being further illustrated the contents of the present invention.
The professional of fields will be appreciated that chemical reaction described in the invention can be used to suitably prepare this
Invention other analogies, and the other methods for being used to prepare analogies of the invention be considered as the scope of the present invention it
It is interior.For example, the synthesis of the analogies of those non-illustrations can successfully be passed through by those skilled in the art according to the present invention
Method of modifying is completed, such as by using other known reagent in addition to described in the invention, or by reaction condition do it is some often
The modification of rule.In addition, reaction disclosed in this invention or known reaction condition are also admittedly suitable for the present invention, other are similar
The preparation of type analogies.
The professional technicians of fields it should also be recognized that: individual analogies that 1-3 of the embodiment of the present invention is proved
Feature (catalytic performance test method, test result used by target simulation object 1-3), the mould of other those non-illustrations of the invention
Quasi- object similarly has, and equally has significant catalytic action in terms of Catalytic Proton acid is reduced into hydrogen.Analogies of the invention
(the target simulation object comprising illustration and non-illustration) only makees change or replacement to target simulation object in embodiment, will not be to it
Effect in terms of Catalytic Proton acid is reduced into hydrogen obviously have detrimental effect.
In the embodiment listed by the present invention, used chemical raw material (chemical raw material i.e. listed in Table) by gram be in terms of
Measure unit.
Embodiment 1
The double phosphine chelatings of the amido of nitrogen-containing hetero trimethylene base replace the photochemical syntheses method of iron iron hydrogenation enzyme mimics 1, chemistry
Formula is Fe2(μ-SCH2N(Ph)CH2S-μ)(CO)4{k2-(Ph2P)2N(CH2)3NMe2, preparation process is as follows:
Specific preparation process is as follows for it:
By 0.070g (0.15mmol) Fe2{μ-SCH2N(Ph)CH2S-μ}(CO)6(0.18mmol, 1.2 times are worked as with 0.085g
Amount) (Ph2P)2N(CH2CH2CH2NMe2) mixture be added to in stirring elongated Schlenk bottles of magneton, substitute nitrogen 3
After secondary, simultaneously stirring and dissolving obtains light red solution to injection 90mL toluene；It the use of power is 20W and wavelength under conditions of being protected from light
For the above-mentioned mixed solution of LED light vertical irradiation of 365nm, room temperature irradiates 2h, and red solution becomes dark red solution, TLC monitoring
Reaction raw materials disappear, and stop reaction, and toluene solvant is sloughed in revolving decompression, extract residue with methylene chloride, are two with solvent
Chloromethanes: methanol (v:v=20:1) carries out preparative thin-layer chromatography chromatographic isolation, collects rufous mass-tone band, obtains peony
Solid is target simulation object 1 (0.112g, yield 85.3%).
The structural characterization data of target simulation object 1 are as follows: FT-IR (KBr disk) νC≡O/cm-1:2018(vs),1953
(vs),1907(m)；31P-NMR(243MHz,CDCl3, 85%H3PO4)δp/ppm:111.27(br s,apical-basal
Isomer, 30%), 97.89 (s, basal-basal isomer, 70%).
In conjunction with above data and as shown in Figure 1, the infrared spectroscopy of target simulation object 1 is in 2018,1953,1907cm-1At three
Show the feature stretching vibration absworption peak of iron carbonyl in two iron, two sulphur skeleton, and its first infrared absorption peak is located at
2018cm-1Place show bidentate ligand chelate same iron atom presence (its first characteristic IR absorbance peaks be 2020cm-1
Left and right), i.e. amido biphosphine ligand chelating replaces being successfully generated for analogies 1.Further, as shown in Figure 2, target simulation object 1
Nuclear magnetic resonance phosphorus spectrum a width unimodal and unimodal phosphorus signal are set forth at 111.27 and 97.89ppm two, show mould
There are two types of isomers to exist for quasi- object 1, i.e., in the molecule in amido biphosphine ligand two phosphorus atoms with apical-basal and
Two kinds of geometric configuration chelating ligands of basal-basal are in same iron atom.
The electrochemical cyclic voltammetry of target simulation object 1 is tested:
The experiment utilizes on CHI 660E electrochemical instrument using the glass-carbon electrode of 3mm diameter
To electrode, with non-aqueous Ag/AgNO3(0.01M AgNO3/0.1M n-Bu4NPF6/CH3It CN is) three electrode body of classics of reference electrode
It ties up in cylindrical groove and is measured under nitrogen atmosphere；Will be polished glass carbon before each test with 0.05 μm of aluminum oxide powder
Then electrode uses ultrasonic cleaning, last acetone rinsing, cold wind drying in water；The solvent of test system is the second of chromatographically pure
Nitrile, analogies 1 are 1mmol/L, and supporting electrolyte is the n-Bu for being 0.1mol/L with concentration4NPF6, Bronsted acid 0,2,4,6,8,
10mmol/L acetic acid；Test gained current potential is the reduction potential corrected through ferrocene.
From the figure 3, it may be seen that the catalytic performance of analogies 1 is showed themselves in that in the electro-chemical test body containing 1mmol/L analogies 1
In system, with concentration is 0,2,4,6,8,10mmol/L acetic acid be gradually added into, reduction potential EpIt is held for the peak current of -2.12V
Height of continuing rising, corresponding spike potential have slight negative shifting, and this phenomenon is exactly the notable feature of homogeneous catalysis liberation of hydrogen, shows that it has electricity
Catalytic Proton is reduced into the ability of hydrogen.At the same time, reduction current i of the analogies 1 in non-protonation acidpFor 27.76 μ A,
And the catalytic current i when 10mM acetic acid is as Bronsted acidcatFor 322.08 μ A, according to the calculating of evolving hydrogen reaction catalytic efficiency TOF
Formula kobs(TOF)=1.94 ν (icat/ip)2, can obtain its theory catalytic efficiency TOF is 26.12s-1。
Embodiment 2
The double phosphine chelatings of amido containing ethylene group replace the photochemical syntheses method of iron iron hydrogenation enzyme mimics 2, and chemical formula is
Fe2(μ-SCH2CH2S-μ)(CO)4{k2-(Ph2P)2N(CH2)3NMe2, preparation process is as follows:
Specific preparation process is as follows for it:
By 0.930g (0.25mmol) Fe2{μ-SCH2CH2S-μ}(CO)6With 0.142g (0.30mmol, 1.2 times of equivalents)
(Ph2P)2N(CH2CH2CH2NMe2) mixture be added to in stirring elongated Schlenk bottles of magneton, substitute nitrogen 3 times
Afterwards, simultaneously stirring and dissolving obtains light red solution to injection 100mL toluene；Under conditions of being protected from light, using power be 20W and wavelength is
The above-mentioned mixed solution of LED light vertical irradiation of 365nm, room temperature irradiate 3h, and red solution becomes dark red solution, and TLC monitoring is anti-
It answers raw material to disappear, stops reaction, toluene solvant is sloughed in revolving decompression, is extracted residue with methylene chloride, is dichloro with solvent
Methane: methanol (v:v=10:1) carries out preparative thin-layer chromatography chromatographic isolation, collects green mass-tone band, obtains green solid i.e.
For target simulation object 2 (0.056g, yield 28.6%).
The structural characterization data of target simulation object 2 are as follows: FT-IR (KBr disk) νC≡O/cm-1:2012(vs),1945
(vs),1933(vs),1899(s)；31P-NMR(243MHz,CDCl3, 85%H3PO4)δp/ppm:113.69(br s,apical-
Basal isomer, 90%), 103.91 (s, basal-basal isomer, 10%).
In conjunction with above data and as shown in Figure 1, the infrared spectroscopy of target simulation object 2 is in 2012,1945,1933,1899cm-1
The feature stretching vibration absworption peak of iron carbonyl in two iron, two sulphur skeleton, and its first infrared absorption peak position are shown everywhere
In 2012cm-1Place show bidentate ligand chelate same iron atom presence (its first characteristic IR absorbance peaks be 2020cm-1Left and right), i.e. the successful synthesis of amido biphosphine ligand chelating substitution analogies 2.Further, as shown in Figure 2, target simulation object 2
Nuclear magnetic resonance phosphorus spectrum a width unimodal and unimodal phosphorus signal are set forth at 113.69 and 103.91ppm two, show
There are two types of isomers to exist for analogies 2, i.e., in the molecule in amido biphosphine ligand two phosphorus atoms with apical-basal and
Two kinds of geometric configuration chelating ligands of basal-basal are in same iron atom.
The electrochemical cyclic voltammetry of target simulation object 2 is tested:
The experiment utilizes on CHI 660E electrochemical instrument using the glass-carbon electrode of 3mm diameter
To electrode, with non-aqueous Ag/AgNO3(0.01M AgNO3/0.1M n-Bu4NPF6/CH3It CN is) three electrode body of classics of reference electrode
It ties up in cylindrical groove and is measured under nitrogen atmosphere；Will be polished glass carbon before each test with 0.05 μm of aluminum oxide powder
Then electrode uses ultrasonic cleaning, last acetone rinsing, cold wind drying in water；The solvent of test system is the second of chromatographically pure
Nitrile, analogies 2 are 1mmol/L, and supporting electrolyte is the n-Bu for being 0.1mol/L with concentration4NPF6, Bronsted acid 0,2,4,6,8,
10mmol/L acetic acid；Test gained current potential is the reduction potential corrected through ferrocene.
As shown in Figure 4, the catalytic performance of analogies 2 is showed themselves in that in the electro-chemical test body containing 1mmol/L analogies 2
In system, with concentration is 0,2,4,6,8,10mmol/L acetic acid be gradually added into, reduction potential EpIt is held for the peak current of -2.25V
Height of continuing rising, corresponding spike potential have slight negative shifting, and this phenomenon is exactly the notable feature of homogeneous catalysis liberation of hydrogen, shows that it has electricity
Catalytic Proton is reduced into the ability of hydrogen.At the same time, reduction current i of the analogies 2 in non-protonation acidpFor 28.00 μ A,
And the catalytic current i when 10mM acetic acid is as Bronsted acidcatFor 232.40 μ A, according to the calculating of evolving hydrogen reaction catalytic efficiency TOF
Formula kobs(TOF)=1.94 ν (icat/ip)2, can obtain its theory catalytic efficiency TOF is 13.36s-1。
Embodiment 3
The double phosphine chelatings of the amido of the base of trimethylene containing oxa- replace the photochemical syntheses method of iron iron hydrogenation enzyme mimics 3, chemistry
Formula is Fe2(μ-SCH2OCH2S-μ)(CO)4{k2-(Ph2P)2N(CH2)3NMe2, preparation process is as follows:
Specific preparation process is as follows for it:
By 0.059g (0.15mmol) Fe2{μ-SCH2OCH2S-μ}(CO)6With 0.085g (0.18mmol, 1.2 times of equivalents)
(Ph2P)2N(CH2CH2CH2NMe2) mixture be added to in stirring elongated Schlenk bottles of magneton, substitute nitrogen 3 times
Afterwards, simultaneously stirring and dissolving obtains light red solution to injection 90mL toluene；Under conditions of being protected from light, using power be 20W and wavelength is
The above-mentioned mixed solution of LED light vertical irradiation of 365nm, room temperature irradiate 2h, and red solution becomes dark red solution, and TLC monitoring is anti-
It answers raw material to disappear, stops reaction, toluene solvant is sloughed in revolving decompression, is extracted residue with methylene chloride, is dichloro with eluant, eluent
Methane: methanol (v:v=20:1) mixed solvent is carried out silica gel column chromatography separation, is collected red mass-tone band, is obtained red
Color solid is target simulation object 3 (0.103g, yield 85.5%).
The structural characterization data of target simulation object 3 are as follows: FT-IR (KBr disk) νC≡O/cm-1:2020(vs),1948
(vs),1906(m)；31P-NMR(243MHz,CDCl3, 85%H3PO4)δp/ppm:114.22(s,apical-basal
Isomer, 28%), 97.75 (s, basal-basal isomer, 72%).
In conjunction with above data and as shown in Figure 1, the infrared spectroscopy of target simulation object 3 is in 2020,1948,1906cm-1At three
Show the feature stretching vibration absworption peak of iron carbonyl in two iron, two sulphur skeleton, and its first infrared absorption peak is located at
2020cm-1Place show bidentate ligand chelate same iron atom presence (its first characteristic IR absorbance peaks be 2020cm-1
Left and right), i.e. the successful synthesis of amido biphosphine ligand chelating substitution analogies 3.Further, as shown in Figure 2, target simulation object 3
Nuclear magnetic resonance phosphorus spectrum unimodal phosphorus signal is given at 114.22 and 97.75ppm two, show analogies 3 there are two types of different
Structure body exists, i.e., two phosphorus atoms are several with apical-basal and two kinds of basal-basal in amido biphosphine ligand in the molecule
What configuration chelating ligands is in same iron atom.
The electrochemical cyclic voltammetry of target simulation object 3 is tested:
The experiment utilizes on CHI 660E electrochemical instrument using the glass-carbon electrode of 3mm diameter
To electrode, with non-aqueous Ag/AgNO3(0.01M AgNO3/0.1M n-Bu4NPF6/CH3It CN is) three electrode body of classics of reference electrode
It ties up in cylindrical groove and is measured under nitrogen atmosphere；Will be polished glass carbon before each test with 0.05 μm of aluminum oxide powder
Then electrode uses ultrasonic cleaning, last acetone rinsing, cold wind drying in water；The solvent of test system is the second of chromatographically pure
Nitrile, analogies 3 are 1mmol/L, and supporting electrolyte is the n-Bu for being 0.1mol/L with concentration4NPF6, Bronsted acid 0,2,4,6,8,
10mmol/L acetic acid；Test gained current potential is the reduction potential corrected through ferrocene.
As shown in Figure 5, the catalytic performance of analogies 3 is showed themselves in that in the electro-chemical test body containing 1mmol/L analogies 3
In system, with concentration is 0,2,4,6,8,10mmol/L acetic acid be gradually added into, reduction potential EpIt is held for the peak current of -2.17V
Height of continuing rising, corresponding spike potential have slight negative shifting, and this phenomenon is exactly the notable feature of homogeneous catalysis liberation of hydrogen, shows that it has electricity
Catalytic Proton is reduced into the ability of hydrogen.At the same time, reduction current i of the analogies 3 in non-protonation acidpFor 13.18 μ A,
And the catalytic current i when 10mM acetic acid is as Bronsted acidcatFor 315.76 μ A, according to the calculating of evolving hydrogen reaction catalytic efficiency TOF
Formula kobs(TOF)=1.94 ν (icat/ip)2, can obtain its theory catalytic efficiency TOF is 111.35s-1。
Embodiment 4
The double phosphine chelatings of the amido of nitrogen-containing hetero trimethylene base replace the photochemical syntheses method of iron iron hydrogenation enzyme mimics 4, chemistry
Formula is Fe2(μ-SCH2N(Ph)CH2S-μ)(CO)4{k2-(Ph2P)2N(CH2)3Me }, preparation process is as follows:
Specific preparation process is as follows for it:
By 0.070g (0.15mmol) Fe2{μ-SCH2N(Ph)CH2S-μ}(CO)6With 0.099g (0.225mmol, 1.5 times
Equivalent) (Ph2P)2N(CH2CH2CH2Me mixture) is added in elongated Schlenk bottles with stirring magneton, substitutes nitrogen 3
After secondary, simultaneously stirring and dissolving obtains light red solution to injection 90mL toluene；It the use of power is 20W and wavelength under conditions of being protected from light
For the above-mentioned mixed solution of LED light vertical irradiation of 365nm, room temperature irradiates 2h, and red solution becomes dark red solution, TLC monitoring
Reaction raw materials disappear, and stop reaction, and toluene solvant is sloughed in revolving decompression, extract residue with a small amount of methylene chloride, use eluant, eluent
For methylene chloride: petroleum ether (v:v=2:3) mixed solvent is carried out silica gel column chromatography separation, collects rufous mass-tone
Band, obtaining dark red solid is target simulation object 4 (0.089g, yield 70.2%).
The structural characterization data of target simulation object 4 are as follows: FT-IR (KBr disk) νC≡O/cm-1:2019(vs),1954
(vs),1910(m)；31P-NMR(243MHz,CD3COCD3, 85%H3PO4)δp/ppm:110.81(br s,apical-basal
Isomer, 53%), 97.03 (s, basal-basal isomer, 47%).
In conjunction with above data and as shown in Figure 1, the infrared spectroscopy of target simulation object 4 is in 2019,1954,1910cm-1At three
Show the feature stretching vibration absworption peak of iron carbonyl in two iron, two sulphur skeleton, and its first infrared absorption peak is located at
2019cm-1Place show bidentate ligand chelate same iron atom presence (its first characteristic IR absorbance peaks be 2020cm-1
Left and right), i.e. amido biphosphine ligand chelating replaces being successfully generated for analogies 4.Further, as shown in Figure 2, target simulation object 4
Nuclear magnetic resonance phosphorus spectrum a width unimodal and unimodal phosphorus signal are set forth at 110.81 and 97.03ppm two, show mould
There are two types of isomers to exist for quasi- object 4, i.e., in the molecule in amido biphosphine ligand two phosphorus atoms with apical-basal and
Two kinds of geometric configuration chelating ligands of basal-basal are in same iron atom.
Embodiment 5
The double phosphine chelatings of amido containing ethylene group replace the photochemical syntheses method of iron iron hydrogenation enzyme mimics 5, and chemical formula is
Fe2(μ-SCH2CH2S-μ)(CO)4{k2-(Ph2P)2N(CH2)3Me }, preparation process is as follows:
Specific preparation process is as follows for it:
By 0.930g (0.25mmol) Fe2{μ-SCH2CH2S-μ}(CO)6With 0.099g (0.375mmol, 1.5 times of equivalents)
(Ph2P)2N(CH2CH2CH2Me mixture) is added in elongated Schlenk bottles with stirring magneton, after substituting nitrogen 3 times,
Simultaneously stirring and dissolving obtains light red solution to injection 100mL toluene；Under conditions of being protected from light, using power be 20W and wavelength is
The above-mentioned mixed solution of LED light vertical irradiation of 365nm, room temperature irradiate 3h, and red solution becomes dark red solution, and TLC monitoring is anti-
It answers raw material to disappear, stops reaction, toluene solvant is sloughed in revolving decompression, is extracted residue with methylene chloride and is mixed with a small amount of silica gel
Sample is methylene chloride with 150mL eluant, eluent: petroleum ether (v:v=2:3) mixed solvent simultaneously contains 2-3 drop triethylamine, is carried out
Green mass-tone band is collected in silica gel column chromatography separation, and obtaining green solid is that (0.069g, yield are target simulation object 5
36.3%).
The structural characterization data of target simulation object 5 are as follows: FT-IR (KBr disk) νC≡O/cm-1:2016(vs),1959
(vs),1934(vs),1906(vs)；31P-NMR(243MHz,CDCl3, 85%H3PO4)δp/ppm:113.21(br s,
Apical-basal isomer, 90%), 103.31 (s, basal-basal isomer, 10%).
In conjunction with above data and as shown in Figure 1, the infrared spectroscopy of target simulation object 5 is in 2016,1959,1934,1906cm-1
The feature stretching vibration absworption peak of iron carbonyl in two iron, two sulphur skeleton, and its first infrared absorption peak position are shown everywhere
In 2016cm-1Place show bidentate ligand chelate same iron atom presence (its first characteristic IR absorbance peaks be 2020cm-1Left and right), i.e. the successful synthesis of amido biphosphine ligand chelating substitution analogies 5.Further, as shown in Figure 2, target simulation object 5
Nuclear magnetic resonance phosphorus spectrum a width unimodal and unimodal phosphorus signal are set forth at 113.21 and 103.31ppm two, show
There are two types of isomers to exist for analogies 5, i.e., in the molecule in amido biphosphine ligand two phosphorus atoms with apical-basal and
Two kinds of geometric configuration chelating ligands of basal-basal are in same iron atom.
Embodiment 6
The double phosphine chelatings of the amido of the base of trimethylene containing oxa- replace the photochemical syntheses method of iron iron hydrogenation enzyme mimics 6, chemistry
Formula is Fe2(μ-SCH2OCH2S-μ)(CO)4{k2-(Ph2P)2N(CH2)3Me }, preparation process is as follows:
Specific preparation process is as follows for it:
By 0.059g (0.15mmol) Fe2{μ-SCH2OCH2S-μ}(CO)6With 0.099g (0.225mmol, 1.5 times of equivalents)
(Ph2P)2N(CH2CH2CH2Me mixture) is added in elongated Schlenk bottles with stirring magneton, after substituting nitrogen 3 times,
Simultaneously stirring and dissolving obtains light red solution to injection 90mL toluene；Under conditions of being protected from light, using power be 20W and wavelength is
The above-mentioned mixed solution of LED light vertical irradiation of 365nm, room temperature irradiate 2h, and red solution becomes dark red solution, and TLC monitoring is anti-
It answers raw material to disappear, stops reaction, toluene solvant is sloughed in revolving decompression, is extracted residue with a small amount of methylene chloride, is eluted with 150mL
Agent is methylene chloride: petroleum ether (v:v=2:3) mixed solvent simultaneously contains 2-3 drop triethylamine, is carried out silica gel column chromatography
Red mass-tone band is collected in separation, and obtaining red solid is target simulation object 6 (0.048g, yield 41.5%).
The structural characterization data of target simulation object 6 are as follows: FT-IR (KBr disk) νC≡O/cm-1:2020(vs),1949
(vs),1895(m)；31P-NMR(243MHz,CDCl3, 85%H3PO4)δp/ppm:113.51(s,apical-basal
Isomer, 31%), 98.16 (s, basal-basal isomer 69%).
In conjunction with above data and as shown in Figure 1, the infrared spectroscopy of target simulation object 6 is in 2020,1949,1895cm-1At three
Show the feature stretching vibration absworption peak of iron carbonyl in two iron, two sulphur skeleton, and its first infrared absorption peak is located at
2020cm-1Place show bidentate ligand chelate same iron atom presence (its first characteristic IR absorbance peaks be 2020cm-1
Left and right), i.e. the successful synthesis of amido biphosphine ligand chelating substitution analogies 6.Further, as shown in Figure 2, target simulation object 6
Nuclear magnetic resonance phosphorus spectrum unimodal phosphorus signal is given at 113.51 and 98.16ppm two, show analogies 6 there are two types of different
Structure body exists, i.e., two phosphorus atoms are several with apical-basal and two kinds of basal-basal in amido biphosphine ligand in the molecule
What configuration chelating ligands is in same iron atom.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (7)
1. the double phosphine chelatings of the amido of the base containing disulphide bridges replace iron iron to hydrogenate enzyme mimics, which is characterized in that in the analogies
The double phosphines of amido are coordinated in same iron atom in a manner of chelating, and the analogies chemical formula is Fe2(μ-SXS-μ)(CO)4{κ 2 -
(Ph2P)2N (R) }, molecular structural formula is as follows:
；
Wherein X is azepine trimethylene base CH2N(Ph)CH2, ethylene group CH2CH2Or oxa- trimethylene base CH2OCH2；R is N, N- dimethyl-
1- propyl (CH2)3NMe2。
2. the double phosphine chelatings of the amido of the base containing disulphide bridges replace the photochemistry of iron iron hydrogenation enzyme mimics to close as described in claim 1
At method, which comprises the following steps:
(1) two iron, two sulphur, six carbonyl-complexes Fe is weighed2(μ-SXS-μ)(CO)6With the double phosphine (Ph of amido2P)2NR is mixed,
In a nitrogen atmosphere, toluene solvant is injected, magnetic agitation obtains light red liquid；
(2) under conditions of being protected from light, with the above-mentioned solution of LED light vertical irradiation, 2~3h is reacted at room temperature, TLC monitoring reaction raw materials disappear
Until mistake；
(3) vacuum rotary steam removes toluene solvant and obtains crude product, extracts residue with methylene chloride, uses mixed solvent as expansion
Agent or eluant, eluent carry out preparative thin-layer chromatography or column chromatography chromatogram separation, obtain target simulation object；
Wherein X is azepine trimethylene base CH2N(Ph)CH2, ethylene group CH2CH2Or oxa- trimethylene base CH2OCH2；R is N, N- dimethyl-
1- propyl (CH2)3NMe2。
3. the photochemistry that the double phosphine chelatings of the amido of the base according to claim 2 containing disulphide bridges replace iron iron hydrogenation enzyme mimics
Synthetic method, which is characterized in that two iron, two sulphur, six carbonyl-complexes Fe in the step (1)2(μ-SXS-μ)(CO)6It is double with amido
Phosphine (Ph2P)2The mixing ratio of NR and toluene solvant is 0.15~0.25mmol:0.18~0.375mmol:90~100mL.
4. the photochemistry that the double phosphine chelatings of the amido of the base according to claim 3 containing disulphide bridges replace iron iron hydrogenation enzyme mimics
Synthetic method, which is characterized in that the power of LED light used in the step (2) is 20W and wavelength is 365nm.
5. the photochemistry that the double phosphine chelatings of the amido of the base according to claim 4 containing disulphide bridges replace iron iron hydrogenation enzyme mimics
Synthetic method, which is characterized in that the mixed solvent in the step (3) is methylene chloride/petroleum ether mixing that volume ratio is 2:3
Methylene chloride/petroleum ether the mixed liquor or volume ratio that volume ratio of the liquid perhaps containing 2~3 drop triethylamines in 150mL is 2:3 be
The methylene chloride/methanol mixed liquor of 10:1~20:1.
6. the photochemistry that the double phosphine chelatings of the amido of the base according to claim 5 containing disulphide bridges replace iron iron hydrogenation enzyme mimics
Synthetic method, which is characterized in that the preparative thin-layer chromatography in the step (3) is silica G thin-layer chromatography, and column chromatography is 200
~300 mesh silica gel column chromatographies.
7. the double phosphine chelatings of the amido of the base described in claim 1 containing disulphide bridges replace iron iron hydrogenation enzyme mimics in electro-catalysis proton
Acid is reduced into the application in hydrogen.
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